Supporting Information. For. Organic Semiconducting Materials from Sulfur-Hetero. Benzo[k]fluoranthene Derivatives: Synthesis, Photophysical

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1 upporting Information For Organic emiconducting Materials from ulfur-hetero Benzo[k]fluoranthene Derivatives: ynthesis, Photophysical Properties and Thin Film Transistor Fabrication Qifan Yan, Yan Zhou, Ben-Bo Ni, Yuguo Ma,*, Jian Wang,*, Jian Pei*, and Yong Cao Beijing National Laboratory for Molecular ciences (BNLM), Key Laboratories of Bioorganic Chemistry and Molecular Engineering and of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry, Peking University, Beijing , and Institute of Polymer Optoelectronic Materials and Devices, outh China University of Technology, and Key Lab of pecially Functional Materials of Ministry of Education, Guangzhou , China Table of Contents 1. Experimental ection H and 13 C NMR spectra 11 Peking University outh China University of Technology 1

2 1. Experimental ection General Methods. Chemicals were purchased and used as received. All air and water sensitive reactions were performed under nitrogen atmosphere. Toluene and tetrahydrofuran (THF) were distilled from sodium, dichloromethane (DCM) was distilled from CaH 2, methanol (MeOH) was dried over sieves, and nitromethane (MeNO 2 ) was dried over sieves then distilled prior to use. 2,2 -(ethyne-1,2-diyl)bisthiophene was obtained from 2-iodothiophene 128 and 7,9-dipentyl-8H-cyclopenta[α]acenaphthylen-8-one was obtained from acenaphthenequinone followed literature procedure H and 13 C NMR spectra were recorded using CDCl 3 as solvent unless otherwise noted. All chemical shifts were reported in parts per million (ppm), 1 H NMR chemical shifts were referenced to TM (0 ppm) or residual CHCl 3 (7.26 ppm), and 13 C NMR chemical shifts were referenced to CDCl 3 (77.23 ppm) or 1,1,2,2-tetrachloroethane-d 2 (73.70 ppm). Fabrications of Organic Films and OFETs. Organic field-effect transistors based on fluoranthene derivatives 8-11 were fabricated in a top contact configuration. A heavily doped, n-type i wafer was used as the gate electrode and substrate. A thermally grown io 2 layer (ca. 300 nm thick) acted as gate insulator with a unit capacitance of 11 nf cm -2. Prior to the deposition of semiconductors, the i/io 2 substrate was immersed in 10 mg/ml n-octadecyltrichlorosilane (OT) in toluene at 60 o C for 20 min. emiconductors 8-11 were vacuum-evaporated onto i/io 2 substrate at Pa at a rate of 0.1 nm s -1 to form thin films (ca. 50 nm thick) as active layers. ource and drain electrodes (ca. 100 nm thick) were prepared by 2

3 deposition of Au with a shadow mask. The defined channel width (W) and channel length (L) were 100 μm and 10 mm, respectively. Annealing procedure was done before the deposition of Au under nitrogen. Thin films of semiconductors 8-11 were thermally annealed at 240, 235, 230 and 270 o C for 20 min, respectively. Characterization of Thin Film OFETs. The thin films of semiconductors were imaged with tapping mode. The organic transistors were tested under ambient condition at room temperature. Field-effect mobilities (μ FET ) were extracted from the saturation region of I d using the equation I d = (WC i /2L) μ FET (V g V th ) 2. 7,10-dipentyl-8,9-di(2 -thienyl)fluoranthene (2). A solution of 2,2 -(ethyne-1,2-diyl)bisthiophene (0.19 g, 1.0 mmol) in 1,2,4-trimethylbenzene (2 ml) was refluxed for 40 h while 7,9-dipentyl-8H-cyclopenta[a]acenaphthylen-8-one (0.34 g, 1.0 mmol) was added by portions. After the removal of the solvent under reduced pressure, the residue was purified by flash chromatography over silica gel (petroleum ether, and then petroleum ether/dichloromethane = 20/1 as eluent) to afford 2 (0.36 g, 69%) as a light yellow solid, while g of 2,2 -(ethyne-1,2-diyl)bisthiophene was recovered. 1 H NMR (200 MHz, CDCl 3, ppm): δ 8.01 (d, 2H, J = 7.0 Hz), 7.87 (d, 2H, J = 8.0 Hz), (m, 2H), 7.21 (dd, 2H, J = 5.2, 1.4 Hz), 6.89 (dd, 2H, J = 5.2, 3.5 Hz), 6.76 (dd, 2H, J = 3.5, 1.4 Hz), (m, 4H), (m, 4H), (m, 8H), 0.86 (t, 6H, J = 7.0 Hz). 13 C 3

4 NMR (50 MHz, CDCl 3, ppm): δ 141.3, 137.9, 137.7, 137.2, 135.7, 133.6, 130.2, 128.6, 128.2, 126.9, 126.2, 125.5, 123.5, 32.5, 31.6, 29.8, 22.4, M (EI, m/z): 504 (M +, 100%). Anal. Calcd. for C 34 H 34 2 : C, 80.58; H, Found: C, 80.39; H, Br Br 8,9-di(5-bromo-2-thienyl)-7,10-dipentylfluoranthene (3). To a solution of 2 (0.51 g, 1.0 mmol) in dichloromethane (15 ml) was added acetic acid (15 ml). The mixture was cooled to 0 o C, and then N-bromosuccinimide (NB) (0.39 g, 2.2 mmol) was added by portions. The mixture was stirred overnight at room temperature. The organic phase was washed with brine, 2 M aqueous NaOH and NH 4 Cl solutions, respectively, and then dried over MgO 4. After the removal of solvents under reduced pressure, the residue was recrystallized with CH 2 Cl 2 /EtOH to afford 3 as a light yellow solid (0.57 g, 85%). 1 H NMR (200 MHz, CDCl 3, ppm): δ 8.00 (d, 2H, J = 6.8 Hz), 7.87 (d, 2H, J = 8.2 Hz), (m, 2H), 6.90 (d, 2H, J = 3.8 Hz), 6.54 (d, 2H, J = 3.8 Hz), (m, 4H), (m, 4H), (m, 8H), 0.91 (t, 6H, J = 7.0 Hz). 13 C NMR (50 MHz, CDCl 3, ppm): δ 141.3, 137.9, 137.7, 137.2, 135.7, 133.6, 130.2, 128.6, 128.2, 126.9, 126.2, 125.5, 123.5, 32.5, 31.6, 29.8, 22.4, M (EI, m/z): 662 (M + ), 664 (M + + 2, 100%). Anal. Calcd. for C 34 H 32 Br 2 2 : C, 61.45; H, Found: C, 61.28; H, General Procedure for 4-7. To a mixture of 3 (0.66 g, 1.0 mmol), 4

5 methoxyphenylboronic acid or phenylboronic acid (4.0 mmol), and Pd(PPh 3 ) 4 (70 mg, mmol) in THF (40 ml) was added a solution of K 2 CO 3 (2.8 g, 20 mmol) in H 2 O (10 ml). The mixture was refluxed for overnight. The organic layer was washed with aqueous NH 4 Cl solution, dried over MgO 4. After the removal of solvents under reduced pressure, the residue was recrystallized from CH 2 Cl 2 /EtOH to afford the desired product as a light yellow solid. OMe MeO 8,9-di(5 -(2 -methoxyphenyl)-2 -thienyl)-7,10-dipentylfluoranthene (4). (0.61 g, 85%). 1 H NMR (200 MHz, CDCl 3, ppm): δ 8.03 (d, 2H, J = 7.0 Hz), 7.88 (d, 2H, J = 8.0 Hz), (m, 4H), 7.33 (d, 2H, J = 3.6 Hz), (m, 2H), (m, 4H), 6.76 (d, 2H, J = 3.6 Hz), 3.84 (s, 6H), (m, 4H), (m, 4H), (m, 8H), 0.86 (t, 6H, J = 7.0 Hz). 13 C NMR (75 MHz, CDCl 3, ppm): δ 155.6, 141.3, 139.2, 137.9, 137.6, 137.3, 135.8, 133.5, 130.1, 128.4, 128.1, 128.0, 126.8, 124.6, 123.9, 123.4, 121.1, 112.2, 55.7, 32.6, 31.7, 30.0, 22.6, M (EI, m/z): 718 (M +, 100%). Anal. Calcd. for C 48 H 46 O 2 2 : C, 80.18; H, Found: C, 80.00; H, MeO OMe 5

6 8,9-di(5 -(3 -methoxyphenyl)-2 -thienyl)-7,10-dipentylfluoranthene (5). (0.66 g, 92%). 1 H NMR (300 MHz, CDCl 3, ppm): δ: 8.02 (d, 2H, J = 6.9 Hz), 7.88 (d, 2H, J = 8.1 Hz), (m, 2H), (m, 2H), (m, 6H), (m, 2H), 6.74 (d, 2H, J = 3.6 Hz), 3.82 (s, 6H), (m, 4H), (m, 4H), (m, 8H), 0.86 (t, 6H, J = 7.0 Hz). 13 C NMR (75 MHz, CDCl 3, ppm): δ 160.0, 144.0, 140.9, 137.9, 137.8, 137.0, 136.0, 135.3, 133.5, 130.1, 130.0, 129.6, 128.2, 126.9, 123.5, 122.7, 118.3, 112.8, 111.3, 55.4, 32.5, 31.7, 29.9, 22.5, M (EI, m/z): 718 (M +, 100%). Anal. Calcd. for C 48 H 46 O 2 2 : C, 80.18; H, Found: C, 80.02; H, MeO OMe 8,9-di(5 -(4 -methoxyphenyl)-2 -thienyl)-7,10-dipentylfluoranthene (6). (0.65 g, 91%). 1 H NMR (300 MHz, CDCl 3, ppm): δ 8.03 (d, 2H, J = 7.2 Hz), 7.89 (d, 2H, J = 8.1 Hz), (m, 2H), 7.48 (d, 4H, J = 8.8 Hz), 7.01 (d, 2H, J = 3.4 Hz), 6.88 (d, 4H, J = 8.8 Hz), 6.73 (d, 2H, J = 3.4 Hz), 3.81 (s, 6H), (m, 4H), (m, 4H), (m, 8H), 0.86 (t, 6H, J = 7.0 Hz). 13 C NMR (75 MHz, CDCl 3, ppm): δ 159.1, 144.0, 139.8, 138.0, 137.7, 137.2, 135.6, 130.1, 129.5, 128.2, 127.7, 127.0, 126.9, 123.5, 121.4, 114.4, 55.6, 32.6, 31.7, 29.9, 22.5, M (EI, m/z): 718 (M +, 100 %). Anal. Calcd. for C 48 H 46 O 2 2 : C, 80.18; H, Found: C, 80.06; H,

7 7,10-dipentyl-8,9-di(5 -phenyl-2 -thienyl)fluoranthene (7). (0.56 g, 85%). 1 H NMR (200 MHz, CDCl 3, ppm): δ 8.01 (d, 2H, J = 7.0 Hz), 7.86 (d, 2H, J = 7.8 Hz), (m, 2H), (m, 4H), (m, 4H), (m, 2H), 7.12 (d, 2H, J = 3.9 Hz), 6.76 (d, 2H, J = 3.9 Hz), (m, 4H), (m, 4H), (m, 8H), 0.86 (t, 6H, J = 6.9 Hz). 13 C NMR (50 MHz, CDCl 3, ppm): δ 144.2, 140.9, 138.1, 137.9, 137.2, 135.5, 134.8, 133.6, 130.2, 129.7, 129.0, 128.3, 127.3, 127.0, 125.8, 123.6, 122.5, 32.5, 31.6, 29.9, 22.5, M (EI, m/z): 658 (M +, 100%). Anal. Calcd. for C 46 H 42 2 : C, 83.85; H, Found: C, 83.86; H, General Procedure for To a vigorously stirred solution of 4-7 or 3 (0.20 mmol) in dicholormethane (100 ml) was added dropwise a solution of FeCl 3 (0.19 g, 1.2 mmol) in MeNO 2 (3 ml) at 0 o C. Anhydrous MeOH was added after 30 min and stirred for another 60 min. The mixture was washed with brine, 2 M aquoues NaOH, and NH 4 Cl solution, respectively, and then pushed through a plug of silica gel. After the removal of solvents under reduced pressure, the residue was recrystallized from CHCl 3 /EtOH to give the desired product as a yellow solid. OMe MeO 7

8 Compound 8. (0.11 g, 79%). 1 H NMR (300 MHz, CDCl 3, 55 o C, ppm): δ 8.27 (s, 2H), 8.20 (d, 2H, J = 6.9 Hz), (m, 2H), 7.87 (d, 2H, J = 8.1 Hz), (m, 2H), (m, 2H), (m, 4H), (m, 4H), 4.06 (s, 6H), (m, 8H), (m, 4H), 1.06 (t, 6H, J = 7.4 Hz). 13 C NMR (75 MHz, Cl 2 DCCDCl 2, 95 o C, ppm): δ 156.3, 139.8, 137.4, 135.5, 135.0, 134.6, 134.3, 130.3, 128.9, 128.5, 127.8, 125.9, 123.3, 122.7, 121.1, 119.9, 112.3, 55.7, 32.4, 32.2, 28.0, 22.4, M (EI, m/z): 716 (M +, 100%). HR-M (EI): Calcd. for C 48 H 44 O 2 2 : ; Found: OMe OMe Compound 9. (0.12 g, 82%). 1 H NMR (300 MHz, CDCl 3, 55 o C, ppm): δ (m, 2H), 8.01 (s, 2H), 7.87 (d, 2H, J = 8.1 Hz), (m, 2H), (m, 6H), (m, 2H), (m, 4H), 3.95 (s, 6H), (m, 8H), (m, 4H), 1.06 (t, 6H, J = 7.2 Hz). 13 C NMR (75 MHz, Cl 2 DCCDCl 2, 95 o C, ppm): δ 160.1, 143.8, 137.1, 135.8, 135.2, 134.4, 133.8, 130.3, 129.8, 128.3, 127.8, 126.1, 122.8, 118.9, 117.5, 113.9, 112.1, 55.3, 32.2, 32.1, 27.9, 22.3, M (EI, m/z): 716 (M +, 100%). HR-M (EI): Calcd. for C 48 H 44 O 2 2 : ; Found:

9 MeO OMe Compound 10. (0.14 g, 94%). 1 H NMR (300 MHz, CDCl 3, 55 o C, ppm): δ 8.18 (d, 2H, J = 7.5 Hz), 7.92 (s, 2H), 7.88 (d, 2H, J = 7.8 Hz), 7.80 (d, 4H, J = 9.0 Hz), (m, 2H), 7.04 (d, 4H, J = 9.0 Hz), (m, 4H), 3.91 (s, 6H), (m, 8H), (m, 4H), 1.07 (t, 6H, J = 7.2 Hz). 13 C NMR (75 MHz, Cl 2 DCCDCl 2, 95 o C, ppm): δ 159.8, 143.8, 137.3, 135.5, 135.4, 135.0, 134.3, 130.3, 128.2, 127.8, 127.5, 126.8, 125.9, 122.7, 122.6, 116.3, 114.6, 55.3, 32.2, 32.1, 28.0, 22.3, M (EI, m/z): 716 (M +, 100%). HR-M (EI): Calcd. for C 48 H 44 O 2 2 : ; Found: Compound 11. (0.12 g, 96%). 1 H NMR (300 MHz, CDCl 3, 55 o C, ppm): δ (m, 2H), 8.06 (s, 2H), (m, 6H), (m, 2H), (m, 4H), (m, 2H), (m, 4H), (m, 8H), (m, 4H), 1.07 (t, 6H, J = 7.4 Hz). 13 C NMR (75 MHz, Cl 2 DCCDCl 2, 95 o C, ppm): δ 143.9, 137.2, 135.7, 135.3, 135.0, 134.4, 133.9, 133.8, 130.3, 128.8, 128.3, 127.9, 127.8, 126.2, 126.0, 122.8, 117.4, 32.2, 32.1, 27.9, 22.3, M (EI, m/z): 656 (M +, 100%); HR-M (EI): Calcd. for C 46 H 40 2 : ; Found:

10 Br Br Compound 12. (0.11 g, 85%). 1 H NMR (300 MHz, CDCl 3, 50 o C, ppm): δ (m, 2H), 7.88 (d, 2H, J = 8.1 Hz), (m, 4H), 3.80 (m, 4H), (m, 4H), 1.79 (m, 4H), (m, 4H), 1.04 (t, 6H, J = 7.2 Hz). 13 C NMR (75 MHz, CDCl 3, 50 o C, ppm): δ 137.2, 136.4, 135.7, 134.2, 133.4, 130.7, 128.3, 126.7, 124.6, 123.3, 115.5, 32.5, 32.3, 28.2, 22.8, M (EI, m/z): 660 (M + ), 662 (M + +2, 100%). HR-M (EI): Calcd. for C 34 H 30 Br 2 2 : ; Found:

11 2. Copies of 1 H and 13 C NMR spectra. 1 H NMR spectrum for compound 2 11

12 13 C NMR spectrum for compound 2 12

13 1 H NMR spectrum for compound 3 13

14 13 C NMR spectrum for compound 3 14

15 1 H NMR spectrum for compound 4 15

16 13 C NMR spectrum for compound 4 16

17 1 H NMR spectrum for compound 5 17

18 13 C NMR spectrum for compound 5 18

19 1 H NMR spectrum for compound 6 19

20 13 C NMR spectrum for compound 6 20

21 1 H NMR spectrum for compound 7 21

22 13 C NMR spectrum for compound 7 22

23 1 H NMR spectrum for compound 8 23

24 13 C NMR spectrum of compound 8 24

25 1 H NMR spectrum for compound 9 25

26 13 C NMR spectrum of compound 9 26

27 1 H NMR spectrum for compound 10 27

28 13 C NMR spectrum of compound 10 28

29 1 H NMR spectrum for compound 11 29

30 13 C NMR spectrum for compound 11 30

31 1 H NMR spectra for compound 12 31

32 13 C NMR spectrum for compound 12 32